WO2006126633A1 - Désacylation - Google Patents

Désacylation Download PDF

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Publication number
WO2006126633A1
WO2006126633A1 PCT/JP2006/310448 JP2006310448W WO2006126633A1 WO 2006126633 A1 WO2006126633 A1 WO 2006126633A1 JP 2006310448 W JP2006310448 W JP 2006310448W WO 2006126633 A1 WO2006126633 A1 WO 2006126633A1
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WO
WIPO (PCT)
Prior art keywords
group
organic compound
acylated
exchange resin
unsubstituted
Prior art date
Application number
PCT/JP2006/310448
Other languages
English (en)
Japanese (ja)
Inventor
Hiroshi Suzuki
Original Assignee
National University Corporation Obihiro University Of Agriculture And Veterinary Medicine
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by National University Corporation Obihiro University Of Agriculture And Veterinary Medicine filed Critical National University Corporation Obihiro University Of Agriculture And Veterinary Medicine
Publication of WO2006126633A1 publication Critical patent/WO2006126633A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H17/00—Compounds containing heterocyclic radicals directly attached to hetero atoms of saccharide radicals
    • C07H17/02—Heterocyclic radicals containing only nitrogen as ring hetero atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H1/00—Processes for the preparation of sugar derivatives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H3/00—Compounds containing only hydrogen atoms and saccharide radicals having only carbon, hydrogen, and oxygen atoms
    • C07H3/02—Monosaccharides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H3/00—Compounds containing only hydrogen atoms and saccharide radicals having only carbon, hydrogen, and oxygen atoms
    • C07H3/04—Disaccharides

Definitions

  • the present invention relates to a method for producing an organic compound by removing the acyl group from an organic compound in which a hydroxyl group and Z or a thiol group are acylated using a simple deacylation reaction.
  • the acyl group is widely used as a protecting group for alcohols and thiols. Deacylation is performed using a base and often must be neutralized with acid after use (TW Greene and PGM Wuts, PROTECTING GROUPS IN OR GANIC SYNTHESIS Second Edition, JOHN WILEY and SONS INC., (1990), non-patent literature 1). Neutralization requires a lot of labor and produces a large amount of inorganic salt. For compounds that are sensitive to pH, compounds that are highly water-soluble and difficult to extract with organic solvents, and compounds that are difficult to separate from inorganic salts, desolvation using the above bases is not a solution. There are many problems to be done.
  • the object of the present invention is to provide a neutralization treatment that can be applied to compounds that are sensitive to pH, compounds that are highly water-soluble and difficult to extract with an organic solvent, and compounds that are difficult to separate from inorganic salts. It is an object of the present invention to provide a method that can be easily deasserted without the need for the above.
  • the present invention is as follows.
  • the acylated organic compound is a sugar-related compound in which at least part of hydroxyl group and Z or thiol group is sacylated, or at least part of hydroxyl group and z or thiol group is substituted. Or unsubstituted linear or branched alkyl, substituted or unsubstituted alkene, substituted or unsubstituted alkyne, substituted or unsubstituted phenyl, substituted or unsubstituted heteroaromatic, or substituted or unsubstituted heterofatty The method according to [1], which is a tribe.
  • acylated organic compound is a sugar-related compound in which at least a part of hydroxyl groups and Z or thiol groups are acylated.
  • the acyl group strength is at least one selected from the group force comprising acetyl group, benzoyl group, bivaloyl group, chloroacetyl group, dichloroacetyl group, trichloroacetyl group, thioacetyl group, and thiobenzoyl group force [1] to The method according to any one of [3].
  • the acyl group power is a group power consisting of a acetyl group, a chloroacetyl group, a dichloroacetyl group, a trichloroacetyl group, and a thioacetyl group, and is at least one selected from [1] to [3] Method.
  • the target product can be obtained almost quantitatively simply by stirring the coconut resin at room temperature for 30 minutes, filtering off the resin insoluble in methanol, and concentrating the mother liquor.
  • it is particularly effective when synthesizing a compound having a pyridine nitrogen, for example, when there is no need to worry about pH in the post-treatment.
  • the present invention relates to an organic compound in which at least a part of hydroxyl groups and Z or a thiol group are acylated (the acyl compound and the organic compound) are eliminated, and the acylated hydroxyl group is
  • This is a method for producing an organic compound which is an unsubstituted hydroxyl group and z or a thiol group.
  • the present invention is characterized in that the elimination of the acyl group is carried out by bringing the acylated organic compound into contact with a basic ion exchange resin.
  • the acylated organic compound (1) which is a raw material compound in the method of the present invention is an organic compound in which at least a part of hydroxyl groups and Z or thiol groups are acylated.
  • R is, for example, a sugar, a C to C linear alkyl, a C to C branched alkyl, a C
  • any organic compound having an acyl group can be used in the production method of the present invention.
  • the alkyl, haloalkyl, alkene, alkyne, phenyl, heteroaromatic and heteroaliphatic may be unsubstituted or have a substituent.
  • the substituent include an alkoxy group, a thioalkoxy group, a nitro group, a nitroso group, a cyano group, an isocyano group, a halogen group, and a silyl group.
  • the heteroaliphatic includes cyclic heteroaliphatics and linear and branched heteroaliphatics.
  • An acyl organic compound in which R is a sugar is a sugar-related compound.
  • sugar include Monosaccharides such as lucose, galactose, mannose, idose, talose, altrose, their reducing sugars, amino sugars such as sialic acid, sugar chains by the above combinations, C of these sugars
  • Examples include acids, peptides, and polypeptide derivatives.
  • X and X are independently an oxygen or sulfur atom.
  • Y represents C to C linear alkyl, C to C branched alkyl, C to C
  • Aromatics can be mentioned.
  • the alkyl, haloalkyl, alkene, alkyne, phenol, heteroaromatic and heteroaliphatic may be unsubstituted or may have a substituent. Examples of alkyl etc. are the same as R.
  • examples of the asil group include a acetyl group, bezoyl group, bivaloyl group, chloroacetyl group, dichloroacetyl group, trichloroacetyl group, thioacetyl group, and thiobenzoyl group.
  • a basic ion exchange resin has an anion exchange group such as an ammonium salt supported on a polymer compound such as polystyrene, and the counter ion is converted to a hydroxide ion in an alkaline aqueous solution. It is a rosin that shows basicity. It can be said that OH-type anion exchange resin is a solid granular alkali that does not dissolve in water.
  • a typical ion exchange resin is a styrene ion exchange resin, but the ion exchange resin used in the present invention is not limited to a styrene ion exchange resin.
  • Ion exchange resin is generally classified into a cation exchange resin and an anion exchange resin depending on whether it has an acidic group or a basic group. It is divided into strong basic type and weak basic type. Strong basic ion-exchange resins are further classified into type I (which has a slightly higher basicity than type II) and type II, and type I is sometimes referred to as the strongest basic anion exchange resin.
  • any basic ion exchange resin can be used, and the basic ion exchange resin here includes both strong basic type and weak basic type.
  • the deacylation reaction proceeds smoothly under mild reaction conditions at room temperature. From the viewpoint, it is preferably a strongly basic type ion-exchange resin that easily releases hydroxide ions.
  • the exchange group of the strongly basic anion exchange resin (type I) is, for example, RN (CH3) + (fixed ion) + OH (counter ion).
  • the counter ion of the ion-exchange resin is an anion other than a hydroxide ion, it can be applied to the method of the present invention by counter-ion exchange with a metal hydroxide.
  • the basic ion exchange resin used in the method of the present invention may be any fine resin, such as spherical fine particles, films, fibers, etc., if the resin and their reaction residues are insoluble in the reaction solvent. It can be. From the standpoint of easy handling, spherical fine particles are preferred.
  • Examples of basic ion exchange resin include Amberlite IRA-67, Amberlite IRA-4 10, Amberlite IRA-900, Amberlite IRA-743, Amberlyst A-21, Amberlyst A-26 (OH), DOWEX 1X2—100, DOWEX 1X2—200, DOWEX 1X2—400, DOWEX 1X4—50, DO WEX 1X4-100, DOWEX 1X8-100, DOWEX 1X8-200, DOWEX 1X8-400, DOWEX 21K Cl, DOWEX 2X8—100, DOWEX 2X8—200, DOWEX 22—Cl, DOWEX MARAT HON A, DOWEX MARATHON A2, DOWEX 550A OH, DOWEX 66, DOWEX M ARATHON WBA, DOWEX WGR-2, Dulite A-7, and the like.
  • the deacylation reaction of the present invention is suitably performed in the presence of a solvent.
  • a solvent for example, polar solvents such as water and alcohol (for example, methanol, ethanol, etc.) are desirable.
  • rosin and their reaction residues are insoluble, it is also possible to use, ⁇ -dimethylformamide or dimethyl sulfoxide as a solvent.
  • toluene, benzene, hexane, jetyl ether, tetrahydrofuran, dioxane, etc. are used as solvents. It can also be used as
  • the amount of ion exchange resin used is appropriately determined in consideration of the type of ion exchange resin, the type of organic compound, the type of acyl group, the degree of acyl group (the number of acyl groups per molecule of the organic compound), etc. can do.
  • the amount of ion exchange resin used is suitably 2 to 6 times the mass of the substrate (an acylated organic compound), for example. However, it is not limited to this range.
  • the acylated organic compound is a saccharide-related compound
  • the saccharide is deacylated.
  • the substrate the compound related to the acylyl sucrose.
  • a mass obtained by adding the number of sugars to the weight of sallow to be used for monosaccharides can be used.
  • the temperature and time of the deacylation reaction can be appropriately selected according to the type of the acylation organic compound and the ion exchange resin.
  • Deacylation can usually be performed at room temperature, for example, in the range of 10-30 ° C.
  • the time for the deacylation reaction is, for example, in the range of 10 minutes to 6 hours, and preferably in the range of 30 minutes to 3 hours.
  • Example 1 was followed except that octacacetyl sucrose (1.00 g, 1.47 mmol), Amberlite A-26 (OH) (6.00 g) and the reaction time was 2 hours. Saccharose (0.45 g, 89%) was obtained.
  • the present invention can be used in the field of organic synthesis.

Abstract

L'invention concerne un procédé pour la production d'un composé organique ayant un ou plusieurs groupes hydroxyles et/ou thiols libres en soumettant un composé organique dont les groupes hydroxyles et/ou thiols sont au moins en partie acylés (ci-après appelé 'composé organique acylé') à une désacylation, ladite désacylation étant effectuée en mettant le composé organique acylé en contact avec une résine échangeuse d'ions basique. L'invention concerne un procédé de désacylation lequel est applicable même à des composés sensibles au pH, à des composés peu extractibles avec un solvant organique à cause de leur solubilité élevée dans l'eau et à des composés peu séparables de sels inorganiques et lequel permet une désacylation facile et simple sans neutralisation.
PCT/JP2006/310448 2005-05-26 2006-05-25 Désacylation WO2006126633A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2005-153901 2005-05-26
JP2005153901 2005-05-26

Publications (1)

Publication Number Publication Date
WO2006126633A1 true WO2006126633A1 (fr) 2006-11-30

Family

ID=37452057

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2006/310448 WO2006126633A1 (fr) 2005-05-26 2006-05-25 Désacylation

Country Status (1)

Country Link
WO (1) WO2006126633A1 (fr)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60163832A (ja) * 1984-02-03 1985-08-26 Nisshin Oil Mills Ltd:The グリセリドの加水分解法
JPH02292295A (ja) * 1989-04-22 1990-12-03 Behringwerke Ag エトポシドの製造方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60163832A (ja) * 1984-02-03 1985-08-26 Nisshin Oil Mills Ltd:The グリセリドの加水分解法
JPH02292295A (ja) * 1989-04-22 1990-12-03 Behringwerke Ag エトポシドの製造方法

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